Kinetics of the acid-catalyzed hydrolysis of tetraethoxysilane (TEOS) by 29Si NMR spectroscopy and mathematical modeling

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dc.contributor.authorEcheverría Morrás, Jesús
dc.contributor.authorMoriones Jiménez, Paula
dc.contributor.authorArzamendi Manterola, Gurutze
dc.contributor.authorGarrido Segovia, Julián José
dc.contributor.authorGil Idoate, María José
dc.contributor.authorCornejo Ibergallartu, Alfonso
dc.contributor.authorMartínez Merino, Víctor
dc.contributor.departmentQuímica Aplicadaes_ES
dc.contributor.departmentKimika Aplikatuaeu
dc.contributor.departmentInstitute for Advanced Materials and Mathematics - INAMAT2en
dc.date.accessioned2024-01-17T19:15:58Z
dc.date.available2024-01-17T19:15:58Z
dc.date.issued2018
dc.date.updated2024-01-17T19:00:51Z
dc.description.abstractTetraethoxysilane (TEOS) is widely used to synthesize siliceous material by the sol–gel process. However, there is still some disagreement about the nature of the limiting step in the hydrolysis and condensation reactions. The goal of this research was to measure the variation in the concentration of intermediates formed in the acid-catalyzed hydrolysis by 29Si NMR spectroscopy, to model the reactions, and to obtain the rate constants and the activation energy for the hydrolysis and early condensation steps. We studied the kinetics of TEOS between pH 3.8 and 4.4, and four temperature values in the range of 277.2–313.2 K, with a TEOS:ethanol:water molar ratio of 1:30:20. Both hydrolysis and the condensation rate speeded up with the temperature and the concentration of oxonium ions. The kinetic constants for hydrolysis reactions increased in each step kh1 < kh2 < kh3 < kh4, but the condensation rate was lower for dimer formation than for the formation of the fully hydrolyzed Si(OH)4. The system was described according to 13 parameters: six of them for the kinetic constants estimated at 298.2 K, six to the activation energies, and one to the equilibrium constant for the fourth hydrolysis. The mathematical model shows a steady increase in the activation energy from 34.5 kJ mol−1 for the first hydrolysis to 39.2 kJ mol−1 in the last step. The activation energy for the condensation reaction from Si(OH)4 was ca. 10 kJ mol−1 higher than the largest activation energy in the hydrolytic reactions. The decrease in the net positive charge on the Si atom contributes to the protonation of the ethoxy group and makes it a better leaving group.en
dc.description.sponsorshipThis work was supported by Ministerio de Economía, Industria y Competitividad (MAT2016-78155-C2-2-R). PM is thankful to the Departamento de Industria y Tecnología, Comercio y Trabajo of Navarre Government for a fellowship.en
dc.format.mimetypeapplication/pdfen
dc.format.mimetypeapplication/msworden
dc.identifier.citationEcheverría, J.C., Moriones, P., Arzamendi, G., Garrido, J.J., Gil, M.J., Cornejo, A., Martínez-Merino, V. (2018) Kinetics of the acid-catalyzed hydrolysis of tetraethoxysilane (TEOS) by 29Si NMR spectroscopy and mathematical modeling. Journal of Sol-Gel Science and Technology, 86(2), 316-328. https://doi.org/10.1007/s10971-018-4637-7.en
dc.identifier.doi10.1007/s10971-018-4637-7
dc.identifier.issn0928-0707
dc.identifier.urihttps://academica-e.unavarra.es/handle/2454/47069
dc.language.isoengen
dc.publisherSpringeren
dc.relation.ispartofJournal of Sol-Gel Science and Technology (2018) 86, 316–328en
dc.relation.projectIDinfo:eu-repo/grantAgreement/MINECO//MAT2016-78155-C2-2-R/
dc.relation.publisherversionhttps://doi.org/10.1007/s10971-018-4637-7
dc.rights© Springer Science+Business Media, LLC, part of Springer Nature 2018en
dc.rights.accessRightsinfo:eu-repo/semantics/openAccess
dc.subjectMathematical modellingen
dc.subjectKinetic constantsen
dc.subjectTEOSen
dc.subject29Si NMRen
dc.subjectpH-independent rate constantsen
dc.subjectActivation energyen
dc.titleKinetics of the acid-catalyzed hydrolysis of tetraethoxysilane (TEOS) by 29Si NMR spectroscopy and mathematical modelingen
dc.typeinfo:eu-repo/semantics/article
dc.type.versioninfo:eu-repo/semantics/acceptedVersion
dspace.entity.typePublication
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